CN117239103B - High-nickel ternary positive electrode material, preparation method thereof and lithium ion battery - Google Patents
High-nickel ternary positive electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 48
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 5
- 239000011669 selenium Substances 0.000 claims abstract description 47
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 45
- 238000005245 sintering Methods 0.000 claims abstract description 34
- 239000010405 anode material Substances 0.000 claims abstract description 17
- 239000010406 cathode material Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000009826 distribution Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 37
- 239000002243 precursor Substances 0.000 claims description 37
- 238000000149 argon plasma sintering Methods 0.000 claims description 18
- 239000011159 matrix material Substances 0.000 claims description 16
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 150000002696 manganese Chemical class 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 229940065287 selenium compound Drugs 0.000 claims description 5
- 150000003343 selenium compounds Chemical class 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 14
- 239000007790 solid phase Substances 0.000 abstract description 3
- 229940091258 selenium supplement Drugs 0.000 description 31
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 21
- 239000000203 mixture Substances 0.000 description 17
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 229940044175 cobalt sulfate Drugs 0.000 description 12
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 12
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 12
- 229940099596 manganese sulfate Drugs 0.000 description 12
- 235000007079 manganese sulphate Nutrition 0.000 description 12
- 239000011702 manganese sulphate Substances 0.000 description 12
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 12
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 12
- 229940053662 nickel sulfate Drugs 0.000 description 12
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000010280 constant potential charging Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000338 selenium disulfide Inorganic materials 0.000 description 1
- JNMWHTHYDQTDQZ-UHFFFAOYSA-N selenium sulfide Chemical compound S=[Se]=S JNMWHTHYDQTDQZ-UHFFFAOYSA-N 0.000 description 1
- 229960005265 selenium sulfide Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to the technical field of lithium ion battery materials, and discloses a high-nickel ternary positive electrode material. Selenium is doped in the high-nickel ternary positive electrode material, and Li is coated on the surface of the high-nickel ternary positive electrode material 3 B 5 S 9 The method comprises the steps of carrying out a first treatment on the surface of the The concentration of doped selenium is in a 'low concentration-high concentration-low concentration' circulation distribution from the innermost layer to the outermost layer of the high-nickel ternary cathode material. The high-nickel ternary anode material is prepared by adopting a solid-phase sintering and rapid sintering combined process. After the positive electrode material is assembled into the battery, the multiplying power performance and the cycle performance of the battery can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to modification of a high-nickel ternary positive electrode material of a lithium ion battery.
Background
Lithium ion batteries are widely used in the fields of portable electronic devices, power automobiles, aerospace and the like due to their high energy density and long cycle life. The high-nickel ternary positive electrode material is paid attention to due to higher energy density and lower cost, however, the high-nickel ternary positive electrode material is poor in structural stability and severe in surface side reaction, and further development and application are seriously hindered. The modification research on the high-nickel ternary cathode material mainly focuses on doping, cladding and the like.
Disclosure of Invention
The first object of the invention is to provide a high nickel ternary positive electrode material.
The second object of the invention is to provide a preparation method of the high-nickel ternary cathode material.
A third object of the present invention is to provide a lithium ion battery.
In order to achieve the above object, the present invention provides the following specific technical solutions.
Firstly, the invention provides a high-nickel ternary positive electrode material, selenium is doped in the high-nickel ternary positive electrode material, and Li is coated on the surface of the high-nickel ternary positive electrode material 3 B 5 S 9 。
In a further preferred embodiment, the high nickel ternary positive electrode material has a molecular formula of LiNi x Co y Mn z Se p (OH) 2 @Li 3 B 5 S 9 Wherein x is more than or equal to 0.7 and less than 1, and y is more than or equal to 0 and less than or equal to 0<0.3，0＜z<0.3，x+y+z+p=1，p≠0。
In a further preferred embodiment, the concentration of selenium in the high-nickel ternary cathode material is in a "low concentration-high concentration-low concentration" cyclic distribution from the innermost layer to the outermost layer of the high-nickel ternary cathode material.
Further preferably, in the low concentration doped region of selenium, the molar ratio of selenium to total transition metal ions in the region is X1, and X1 is more than 0 and less than or equal to 0.2%; in the high-concentration doped area of selenium, the molar ratio of selenium to total transition metal ions in the area is X2, and X2 is more than 0 and less than or equal to 0.25 percent; the concentration of selenium in the low concentration doped region of selenium is lower than the concentration of selenium in the high concentration doped region of selenium.
In a further preferred scheme, the concentration of selenium in the innermost layer and the outermost layer of the high-nickel ternary cathode material is low, and the selenium is doped in a laser sintering mode.
Secondly, the invention provides a preparation method of the high-nickel ternary positive electrode material, which comprises the following steps:
step S1, mixing nickel salt, cobalt salt, manganese salt and selenium compound, and performing laser sintering to obtain a precursor I;
step S2, mixing the precursor I with nickel salt, cobalt salt, manganese salt and selenium compound, and performing laser sintering to obtain a precursor II; repeating the steps for a plurality of times by analogy to obtain a precursor;
step S3, mixing the precursor obtained in the step S2 with lithium salt, and sintering to obtain a positive electrode material matrix;
step S4, mixing the positive electrode material matrix and Li in the step S3 3 B 5 S 9 And (5) uniformly mixing and sintering at low temperature to obtain the high-nickel ternary anode material.
In a further preferred embodiment, the high nickel ternary positive electrode material has a molecular formula of LiNi x Co y Mn z Se p (OH) 2 @Li 3 B 5 S 9 Wherein x is more than or equal to 0.7 and less than 1, and y is more than or equal to 0 and less than or equal to 0<0.3，0＜z<0.3，x+y+z+p=1，p≠0。
In a further preferred embodiment, the distribution of selenium in the precursor follows a cyclic distribution that exhibits a "low concentration-high concentration-low concentration" from the innermost layer to the outermost layer of the precursor.
Further preferably, in the low concentration doped region of selenium, the molar ratio of selenium to total transition metal ions in the region is X1, and X1 is more than 0 and less than or equal to 0.2%; in the high-concentration doped area of selenium, the molar ratio of selenium to total transition metal ions in the area is X2, and X2 is more than 0 and less than or equal to 0.25 percent; the concentration of selenium in the low concentration doped region of selenium is lower than the concentration of selenium in the high concentration doped region of selenium.
In a further preferred embodiment, the laser sintering described in step S1 and step S2 comprises at least the following conditions: the temperature of the laser sintering is 800-1500 ℃ and the time is 8-20 min.
In a further preferred embodiment, the sintering conditions in step S3 include at least: the temperature is 700-1200 ℃ and the time is 12-20 h.
In a further preferred embodiment, the molar ratio of the precursor to lithium in the lithium salt in step S3 is 0.9-1.2: 1.
in a further preferred scheme, the low-temperature sintering temperature in the step S4 is 400-700 ℃ and the time is 6-10 h.
In a further preferred embodiment, the positive electrode material matrix and Li in step S4 3 B 5 S 9 The molar ratio of (2) is 1:0.01-0.05.
In a further preferred embodiment, the nickel salt, cobalt salt and manganese salt are at least one of sulfate, nitrate and chloride.
In a further preferred embodiment, the selenium compound is at least one of selenium disulfide and selenium dioxide.
In a further preferred embodiment, the lithium salt is one or more of lithium hydroxide, lithium nitrate, lithium sulfate, lithium carbonate, lithium chloride, lithium borate, and lithium oxalate.
In a further preferred embodiment, the Li 3 B 5 S 9 Prepared by the following method: mixing lithium metal, boron powder and sulfur powder to obtain a mixture; sintering the mixture under argon to obtain Li 3 B 5 S 9 A material.
It is further preferable that the molar ratio of lithium metal, boron powder, sulfur powder is 3:5:9.
further preferred sintering conditions of the mixture include at least: the temperature is 800-1000 ℃; the time is 10-36 h.
Based on the same inventive concept, the invention provides a lithium ion battery, which comprises the high-nickel ternary cathode material.
The invention has the following obvious beneficial technical effects:
according to the invention, selenium is doped in the high-nickel ternary positive electrode material, and the concentration of doped element selenium is circularly distributed from the inner core to the surface of the positive electrode material according to the low concentration, high concentration, low concentration, high concentration and low concentration, so that the introduction amount of extra inert cations is reduced, and the activity of the material is ensured. In addition, the cyclic element doping profile can act as a framework support, maximally stabilizing the structure.
In addition, the invention firstly leads the fast ion conductor Li 3 B 5 S 9 As a coating material of the anode material, the contact between the anode material and the electrolyte can be effectively blocked, and a channel for rapid diffusion and conduction of lithium ions is provided, so that the dissolution of transition metal in the anode material and the occurrence of side reaction between the electrode and the electrolyte are greatly reduced.
Doping selenium in the positive electrode material and coating Li on the surface of the positive electrode material 3 B 5 S 9 Coating Li while doping selenium to improve capacity 3 B 5 S 9 The anode material with high capacity, good conductivity and high electrochemical activity can be obtained by rapid diffusion and conduction.
The invention adopts a solid phase sintering and rapid sintering combined process. The laser sintering can quickly heat the material, so that the doping time is greatly shortened; the solid phase sintering anode material can slowly heat by controlling the heating rate, and slow down the diffusion kinetics in the sintering process, so that Li is obtained 3 B 5 S 9 Uniformly coating the surface of the precursor. The two modes are combined, so that the sintering cost can be effectively reduced, the energy consumption is reduced, and meanwhile, the anode material with stable structure and good performance is obtained.
After the positive electrode material provided by the invention is assembled into a battery, the multiplying power performance and the cycle performance of the battery can be effectively improved.
Drawings
Fig. 1 is an SEM image of the coating material obtained in example 1.
Fig. 2 is an SEM image of the high nickel cathode material prepared in example 1.
Fig. 3 is an electrical performance curve of the assembled battery.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
(1) Uniformly mixing lithium metal, boron powder and sulfur powder according to a molar ratio of 3:5:9 to obtain a mixture; and sintering the mixture for 20 hours at 900 ℃ in an argon atmosphere to obtain the coating material.
Fig. 1 is an SEM image of the clad material.
(2) Mixing nickel sulfate, cobalt sulfate and manganese sulfate according to a molar ratio of 9:0.6:0.4, adding selenium dioxide with a total molar amount of 0.1% of nickel, cobalt and manganese, and carrying out laser sintering at 1200 ℃ for 15min to obtain a precursor I; mixing the prepared precursor I with nickel sulfate, cobalt sulfate and manganese sulfate in the molar ratio of 9:0.6:0.4, adding selenium dioxide with the total molar weight of 0.15% of the nickel sulfate, the cobalt sulfate and the manganese sulfate, mixing, and carrying out laser sintering again to obtain a precursor II; and repeating the steps for 5 times similarly to obtain the selenium-doped precursor with the selenium concentration circularly distributed according to the low concentration, the high concentration, the low concentration, the high concentration and the low concentration.
(3) The precursor and lithium hydroxide are mixed according to a mole ratio of 1:1.1, after being uniformly mixed, sintering for 15 hours at 900 ℃ to obtain a positive electrode material matrix.
(4) Mixing the obtained matrix with Li 3 B 5 S 9 And uniformly mixing according to the molar ratio of 1:0.03, and sintering at 600 ℃ for 8 hours to obtain the high-nickel ternary anode material.
FIG. 2 is an SEM image of a high nickel ternary cathode material, from which it can be seen that the cathode material is large particles obtained by agglomeration growth of fine particles, has rough surface, and contains Li 3 B 5 S 9 The surface of the positive electrode material is coated with the coating to fill the surface gap.
Comparative example 1
Comparative example 1 differs from example 1 only in that: uncoated Li 3 B 5 S 9 。
The specific procedure was not followed by steps (1) and (4) in example 1, and the final product corresponded to the positive electrode material base in example 1.
Comparative example 2
Comparative example 2 differs from example 1 only in that: and undoped selenium. The specific process is as follows:
(1) Uniformly mixing lithium metal, boron powder and sulfur powder according to a molar ratio of 3:5:9 to obtain a mixture; and sintering the mixture for 20 hours at 900 ℃ in an argon atmosphere to obtain the coating material.
(2) And (3) carrying out laser sintering on nickel sulfate, cobalt sulfate and manganese sulfate for 15min at 1200 ℃ according to the mol ratio of 9:0.6:0.4 to obtain a precursor.
(3) The precursor and lithium hydroxide are mixed according to a mole ratio of 1:1.1, after being uniformly mixed, sintering for 15 hours at 900 ℃ to obtain a positive electrode material matrix.
(4) Mixing the obtained matrix with Li 3 B 5 S 9 And uniformly mixing according to the molar ratio of 1:0.03, and sintering at 600 ℃ for 8 hours to obtain the high-nickel ternary anode material.
Comparative example 3
Comparative example 3 differs from example 1 in that: the doped selenium is uniformly distributed in the positive electrode material instead of being distributed in a concentration gradient circulation mode.
The specific process is as follows:
(1) Uniformly mixing lithium metal, boron powder and sulfur powder according to a molar ratio of 3:5:9 to obtain a mixture; and sintering the mixture for 20 hours at 900 ℃ in an argon atmosphere to obtain the coating material.
(2) Nickel sulfate, cobalt sulfate, manganese sulfate and selenium dioxide are mixed according to the mol ratio of 9:0.6:0.4:0.6, and then sintering the mixture for 15min at 1200 ℃ to obtain the precursor.
(3) The precursor and lithium hydroxide are mixed according to a mole ratio of 1:1.1, after being uniformly mixed, sintering for 15 hours at 900 ℃ to obtain a positive electrode material matrix.
(4) Mixing the obtained matrix with Li 3 B 5 S 9 And uniformly mixing according to the molar ratio of 1:0.03, and sintering at 600 ℃ for 8 hours to obtain the high-nickel ternary anode material.
Comparative example 4
Comparative example 4 differs from example 1 in that: the positive electrode material is neither doped with selenium nor coated with Li 3 B 5 S 9 。
The specific process is as follows:
(1) Nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to the mole ratio of 9:0.6:0.4, and then carrying out laser sintering at 1200 ℃ for 15min to obtain a precursor.
(2) The precursor and lithium hydroxide are mixed according to a mole ratio of 1:1.1, after being uniformly mixed, sintering the mixture for 15 hours at 900 ℃ to obtain the anode material.
Example 2
(1) Uniformly mixing lithium metal, boron powder and sulfur powder according to a molar ratio of 3:5:9 to obtain a mixture; and sintering the mixture for 10 hours at 800 ℃ in an argon atmosphere to obtain the coating material.
(2) Mixing nickel sulfate, cobalt sulfate and manganese sulfate according to a molar ratio of 8:1:1, adding selenium dioxide with a total molar amount of 0.07% of nickel, cobalt and manganese, and carrying out laser sintering at 800 ℃ for 8min to obtain a precursor I; the prepared precursor I is mixed with a molar ratio of 8:1:1, mixing nickel sulfate, cobalt sulfate and manganese sulfate, adding selenium dioxide with the total molar weight of 0.1% of the nickel sulfate, the cobalt sulfate and the manganese sulfate, mixing, and carrying out laser sintering again to obtain a precursor II; and repeating the steps for 5 times similarly to obtain the selenium-doped precursor with the selenium concentration circularly distributed according to the low concentration, the high concentration, the low concentration, the high concentration and the low concentration.
(3) Taking a precursor and lithium hydroxide according to a mole ratio of 1: and (3) uniformly mixing the materials, and sintering the mixture at 700 ℃ for 12 hours to obtain the anode material matrix.
(4) Mixing the obtained matrix with Li 3 B 5 S 9 And uniformly mixing according to the molar ratio of 1:0.01, and sintering at 400 ℃ for 6 hours to obtain the high-nickel ternary anode material.
Example 3
(1) Uniformly mixing lithium metal, boron powder and sulfur powder according to a molar ratio of 3:5:9 to obtain a mixture; and sintering the mixture for 36 hours at 1000 ℃ in an argon atmosphere to obtain the coating material.
(2) Mixing nickel sulfate, cobalt sulfate and manganese sulfate according to a molar ratio of 7:2:1, adding selenium dioxide with a total molar amount of 0.2% of nickel, cobalt and manganese, and carrying out laser sintering at 1500 ℃ for 20min to obtain a precursor I; the prepared precursor I is mixed with a molar ratio of 7:2:1, mixing nickel sulfate, cobalt sulfate and manganese sulfate, adding selenium dioxide with the total molar weight of 0.25% of the nickel sulfate, the cobalt sulfate and the manganese sulfate, mixing, and carrying out laser sintering again to obtain a precursor II; and repeating the steps for 5 times similarly to obtain the selenium-doped precursor with the selenium concentration circularly distributed according to the low concentration, the high concentration, the low concentration, the high concentration and the low concentration.
(3) Taking a precursor and lithium hydroxide according to a mole ratio of 1:1.2, and sintering the mixture for 20 hours at 1200 ℃ to obtain the anode material matrix.
(4) Mixing the obtained matrix with Li 3 B 5 S 9 And uniformly mixing according to the molar ratio of 1:0.05, and sintering at 700 ℃ for 10 hours to obtain the high-nickel ternary anode material.
The positive electrode materials obtained in examples 1 to 3 and comparative examples 1 to 4 were assembled into batteries in the following manner, respectively: mixing a positive electrode material, a binder PVDF and a conductive agent according to the proportion of 8:1:1, dry-grinding for 10min, adding a solvent NMP, uniformly stirring by using a homogenizer to prepare positive electrode slurry, and uniformly coating the positive electrode slurry on an aluminum foil; taking a metal lithium sheet as a negative electrode; lithium ion secondary electrolyte LB-037 (1M LiPF6 in DEC:EC:EMC =1:1:1 vol%) was used as electrolyte and Celgard2325 as separator to assemble the lithium ion secondary electrolyte into a button cell of LIR 2032.
The electrical properties of the cells were tested as follows: in a constant temperature box at 25 ℃, constant current charging is carried out to a voltage of 4.3V at a rate of 0.1C, constant voltage charging is carried out to a voltage of 0.01C, the constant voltage charging is carried out, then 0.1C is used for discharging to 3V, circulation is carried out twice, then the battery is charged to a voltage of 4.3V at a rate of 0.5C, constant voltage charging is carried out to a voltage of 0.05C, the constant voltage charging is carried out, then 0.5C is used for discharging to 3V, and the charge and discharge capacity is recorded.
Fig. 3 is a graph showing the electrical performance test of the battery, as can be seen from the graph: the batteries assembled by the positive electrode materials in the examples 1-3 have good electrochemical performance and high stability, the specific capacity of the first-cycle discharge of 0.5C is higher and is 190.3 mAh/g at the maximum, and the capacity retention rate after 100 times of circulation under the condition of 0.5C charge and discharge can reach 89.17%. Compared with comparative examples 1 to 4, the positive electrode material obtained in example 1 greatly improved the cycle stability and the first-turn discharge capacity of the battery.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. A high-nickel ternary positive electrode material is characterized in that selenium is doped in the high-nickel ternary positive electrode material, and Li is coated on the surface of the high-nickel ternary positive electrode material 3 B 5 S 9 The method comprises the steps of carrying out a first treatment on the surface of the The concentration of selenium in the high-nickel ternary positive electrode material is circularly distributed from the innermost layer to the outermost layer of the high-nickel ternary positive electrode material in a 'low concentration-high concentration-low concentration';
the preparation method of the high-nickel ternary cathode material comprises the following steps:
step S1, mixing nickel salt, cobalt salt, manganese salt and selenium compound, and performing laser sintering to obtain a precursor I;
step S2, mixing the precursor I with nickel salt, cobalt salt, manganese salt and selenium compound, and performing laser sintering to obtain a precursor II; repeating the steps for a plurality of times by analogy to obtain a precursor; the distribution of selenium in the precursor follows a cyclic distribution of 'low concentration-high concentration-low concentration' from the innermost layer to the outermost layer of the precursor;
step S3, mixing the precursor obtained in the step S2 with lithium salt, and sintering to obtain a positive electrode material matrix;
step S4, mixing the positive electrode material matrix and Li in the step S3 3 B 5 S 9 And mixing uniformly and sintering to obtain the high-nickel ternary anode material.
2. The high nickel ternary cathode material according to claim 1, wherein in the low concentration doped region of selenium, the molar ratio of selenium to total transition metal ions in the region is X1,0 < X1.ltoreq.0.2%; in the high-concentration doped area of selenium, the molar ratio of selenium to total transition metal ions in the area is X2, and X2 is more than 0 and less than or equal to 0.25 percent; the concentration of selenium in the low concentration doped region of selenium is lower than the concentration of selenium in the high concentration doped region of selenium.
3. The high nickel ternary positive electrode material of claim 1, wherein the concentration of selenium in the innermost and outermost layers of the high nickel ternary positive electrode material is low.
4. The high nickel ternary cathode material of claim 1, wherein the laser sintering of step S1 and step S2 comprises at least the following conditions: the temperature of the laser sintering is 800-1500 ℃ and the time is 8-20 min; the sintering conditions in step S3 include at least: the temperature is 700-1200 ℃ and the time is 12-20 h; and in the step S4, the sintering temperature is 400-700 ℃ and the sintering time is 6-10 h.
5. The high nickel ternary cathode material according to claim 1, wherein the cathode material matrix and Li in step S4 3 B 5 S 9 The molar ratio of (2) is 1:0.01-0.05.
6. A lithium ion battery comprising the high nickel ternary cathode material of any one of claims 1-5.
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